Substituted halo pyrazolinones fungicidal agents

ABSTRACT

Fungicidal compositions of and methods of combating fungi using certain halopyrazolinones of the formula IN WHICH EACH X individually stands for a halogen atom, and R stands for a hydrogen atom, alkyl with up to 24 carbon atoms (which may carry at least one substituent selected from halogen atoms and nitro, chlorosulfonyl and nitrile groups), aryl (which may carry at least one substituent selected from halogen atoms, alkyl groups with up to three carbon atoms, and methoxy, ethoxy and nitro groups), a heterocyclic radical (which may carry at least one substituent selected from halogen atoms and lower alkyl groups), alkoxy, nitro, chlorosulfonyl, alkylsulfoxyl, alkylsulfonyl, alkylcarbamidyl, arylcarbamidyl, carbalkoxy, acyl or amidine, some of which are known, which possess FUNGICIDAL PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent Findeisen et a].

SUBSTITUTED HALO PYRAZOLINONES FUNGICIDAL AGENTS Inventors: Kurt Findeisen; Paul-Ernst Frohberger, both of Leverkusen, Germany Assignee: Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany Filed: Nov. 27, 1970 Appl. No.: 93,394

Foreign Application Priority Data Dec. 6, 1969 Germany ..P 19 61 372.0

us. Cl ..42'4/273 Int. Cl. ..A0ln 9/22 Field of Search ..424/273 References Cited OTHER PUBLICATIONS lacs 80 pp. 599- 601 (1958) Jorg. Chem. 31, 2867- 73 (1966) Primary ExaminerJerome D. Goldberg Assistant ExaminerLeonard Schenkman Att0rney-Burgess, Dinklage & Sprung [57] ABSTRACT Fungicidal compositions of and methods of combating fungi using certain halopyrazolinones of the formula in which each X individually stands for a halogen atom, and R stands for a hydrogen atom, alkyl with up to 24 carbon atoms (which may carry at least one substituent selected from halogen atoms and nitro, chlorosulfonyl and nitrile groups), aryl (which may carry at least one substituent selected from halogen atoms, alkyl groups with up to three carbon atoms, andmethoxy, ethoxy and nitro groups), a heterocyclic radical (which may carry at least one substituent selected from halogen atoms and lower alkyl groups), alkoxy, nitro, chlorosulfonyl, alkylsulfoxyl, alkylsulfonyl, alkylcarbamidyl, arylcarbamidyl, carbalkoxy, acyl or amidine, some of which are known, which possess fungicidal properties and which may be produced by tsniiqnalmelhods 8 Claims, No Drawings SUBSTITUTED HALO PYRAZOLINONES FUNGICIDAL AGENTS The present invention relates to and has for its objects the provision of fungicidal compositions of certain halopyrazolinones of the formula in which each X individually stands for a halogen atom, and R stands for a hydrogen atom, alkyl with up to 24 carbon atoms (which may carry at least one substituent selected from halogen atoms and nitro, chlorosulfonyl and nitrile groups), aryl (which may carry at least one substituent selected from halogen atoms, alkyl groups with up to three carbon atoms, and methoxy, ethoxy and nitro groups), a heterocyclic radical (which may carry at least one substituent selected from halogen atoms and lower alkyl groups), alkoxy, nitro, chlorosulfonyl, alkylsulfoxyl, alkylsulfonyl, alkylcarbamidyl, arylcarbamidyl, carbalkoxy, acyl or amidine, some of which are known and which possess fungicidal properties, in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, preferably containing a surface-active agent, and methods for using such compounds in a new way especially for combating fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that fungal plant diseases can be combated by application of chemicals with fungitoxic effectiveness. The most-used agents include the commercial preparations N-trichloromethylthiotetrahydrophthalim ide (E) (see A. R. Kittleson: Science 115,84 (1952), zinc ethylene-1,2-bisdithiocarbamate (B) (see F. W. Heuberger, T. F. Manns: Phytopathology 33, 133 (1943)), tetramethylthiouram disulfide (D) (see German Pat. Specification No. 642,532 and US. Pat. No. 1,972,961), pentachloronitrobenzene (A) (see German Pat. No. 529,665) and zinc dimethyldithiocarbamate (C). These fungicides have a broad activity spectrum but, despite this, they are ineffective, or only slightly effective, against numerous phytopathogenic fungi. These shortcomings, of course restrict their practical usefulness.

The present invention provides a fungicidal composition containing as active ingredient a halopyrazolinone of the formula (I) as defined above, in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

Surprisingly, the halopyrazolinones which can be used according to the invention possess, like the fungicides of the prior art a broad fungitoxic activity spectrum and, in addition, in many cases they exhibit, at the same application concentration, a substantially higher degree of fungitoxic activity than the prior art fungicides. They are therefore superior, on the whole, to the agents known from the prior art; this is especially so in the case of the application of the agents according to the invention for seed treatment and soil treatment. In the concentrations normally used for the control of phytopathogenic fungi they do not damage cultivated plants. They possess only a slight toxicity to wannblooded animals and because they have only a slight odor and are non-irritating to human skin, are consequently easy to handle. They are therefore suitable for practical use as crop protection agents and therefore represent an enrichment of theart.

The halopyrazolinones which can be used according to the in invention, which may also be present in the tautomeric enol form, are defined by the general formula (I). In this formula, each X stands preferably for a fluorine, chlorine or bromine atom, and R stands preferably for a hydrogen atom,alkyl with up to 17 carbon atoms, trichloromethyl, phenyl, methoxy phenyl or nitrophenyl.

As examples of the compounds which can be used according to the invention, there may be mentioned:

3-methyl-4,4-difluoropyrazolinone- (5) 3-methyl-4,4-dibromopyrazolinone-( 5 3-methyl-4,4-dichloropyrazolinone-(5 3-ethyl-4,4-dichloropyrazolinone-( 5 3-ethyl-4,4-dibromopyrazolinone-( 5 3-n-propyl-4,4-dichloropyrazolinone-( 5 3-n-propyl-4,4-dibromopyrazolinone-( 5 3-tert.-butyl-4,4-dichloropyrazolinone-( 5 3-tert.-butyl-4,4-dibromopyrazolinone-( 5 3phenyl-4,4-dichloropyrazolinone-( 5 3-phenyl-4,4-dibromopyrazolinone-(5 3-m-nitIophenyl-4,4-dichloropyrazolinone-( 5 3-m-nitropheny1-4,4-dibromopyrazolinone-( 5 3-p-methoxyphenyl-4,4-dichloropyrazolinone-( 5 3-p-methoxyphenyl-4,4-dibromopyrazolinone-( 5 4 ,4-dichloropyrazolinone-( 5 3-trichloromethyl-4,4-dichloropyrazolinone-( 5 3-heptadecane-4,4-dichloropyrazolinone-( 5 Some of the compounds which can be used according to the invention are already known. (See Journal of the American Chemical Society, Volume 80, pages 599-601 and 5796-5798 (1958) and Journal of Organic Chemistry, Volume 31, pages 2867-2873 (1966)).

Some of the compounds which can be used according to the invention are new, but they can be prepared in a simple manner according to the processes which are known in principle. They are obtained, for example, when either pyrazolidinones or pyrazolinones are reacted. with elemental halogen at temperatures between 0 and C in the presence of inert solvents such as carbon tetrachloride, chloroform, methylene chloride and other halogenated alkanes, as well as halogenated aromatic compounds, such as chlorobenzene and the dichlorobenzenes. The reaction products may be isolated by distilling off the low-boiling solvent, when such is used, or by using just so much of a high-boiling solvent that the reaction products, which frequently are obtained in a good crystalline form, can be suction filtered directly.

The active compounds according to the invention exhibit a strong fungitoxic activity and can be used as crop protection agents, especially for soil treatment, for seed treatment and for the treatment of above-thesoil parts of plants. They are especially effective against Corticium rolfivii, Sclerotim'a sclerotiorum, Verticillium alboatrum, Tlzielaviopsis basicola, Phytophthora cactorum, Fusarium culmorum, Fusarium oxyspomm, Fusarium solani f. pisi, Pythium ultimum, Tilletia caries and bacteria.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e., plant compatible or herbicidally inert) pesticide diluents or extenders, i.e., diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g., conventional pesticide dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance, by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes), parafi'ms (e.g., petroleum fractions), chlorinated aliphatic hydrocarbons (e.g., methylene chloride, etc.), alcohols (e.g., methanol, ethanol, propanol, butanol, etc.), amines (e.g., ethanolamine, etc.), ethers, ether-alcohols (e.g., glycol monomethyl ether, etc.), amides (e.g., dimethyl formamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), ketones (e.g., acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g., kaolins, alumina, silic'a, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g., highly dispersed silicic acid, silicates, e.g., alkali silicates, etc. whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g., surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g., polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkylsulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other fungicides and acaricides, or insecticides, herbicides, bactericides, nematocides, protective substances preventing damage by birds, growth substances, plant nutrients and soil structure improvement agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 percent, and preferably 0.5-90 percent, by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.001-5 percent, preferably 0.05-1 percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixture of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is efiective for the purpose in question and which is generally between about 0.001- percent, and preferably 0.0595 percent, by weight of the mixture.

In the case of seed treatment, there are required, in general, amounts of active compound of 0.01 to 50 g., preferably 0.5 to 5 g., per kilogram of seed.

For soil treatment, amounts of active compound of l to 1000 g., preferably from 10 to 200 g., per cubic meter of soil are generally used.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e., by applying such com pound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e. g., average particle diameter of from 50-100 microns, or even less, i.e., mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-l 6 fluid ounces/acre, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95 percent by weight of active compound or even the percent active substance alone, e.g., about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling fungi, and more particularly methods of combating fungi, which comprise applying to (a) such fungi and (b) the corresponding habitat thereof, i.e., the locus to be protected, a correspondingly combative or toxic amount, i.e., a fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, squirting, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, via dry dressing, moist dressing, wet dressing, paste dressing, incrustations, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding fun- EXAMPLE 2 gicidal activity of such active compounds usable according to the present invention is illustrated, without seed Dressing Test/Bum of Wheat( Seed-borne limitation, by the following examples. MyCOSlS) EXAMPLE 1 5 To produce a suitable dry dressing, the active compound is extended with a mixture of equal parts by Agar Plate Test weight of talc and kieselguhr to give a finely powdered mixture with the desired concentration of the active Test for fungitoxic effectiveness and breadth of the compound g i Wheat seed is contaminated with 5 g. of the chlavent' i l mydospores of T illetia caries per kg of seed. To apply Parts by welght' the dressing, the seed is shaken with the dressing in a (a) 1000 closed lass flask. The seed, on moist loam under a (b) 100 5 cover of a layer of muslin and 2 cm of moderately moist To Produce a sultahle Preparatlon f the actwe compost soil, is exposed to optimum germination con- P P by Welght of the acme compound ditions for the spores for days at 10 C in a refrigerataken up In the stated amount of solvent. tor.

The preparahoh of achve comphuhd added to The germination of the spores on the wheat grains, P P dextrose agar (whlch has beehhquefied by each of which is contaminated with about 100,000 g) Such an amouht that the deslfed concentration spores, is subsequently determined microscopically. 0f actlve comhohhd 1S P h h After through The smaller the number of spores which have ger- Sha g t0 achleve 3 "Inform l p n the actlve minated, the more effective is the active compound. compound, the agar is poured into Petr! (1 Under The active compounds, the concentrations of the acsterile conditions. When the mlxture Of substrate and tive compounds in the dressing, the amounts of active compound has solidified, test fungi from pure dressing used and the percentage spore germination cultures are inoculated on to it in small discs of 5 mm can be seen from the following Table 2: diameter. The Petri dishes remain at 20 C for 3 days TABLE 2 for incubation. S d D After this time, the inhibiting action of the active ee ressmg test/bum Ofwheat compound on the mycelium growth is determined in Concentration Amoumof Spore categories, taking into account the untreated control. 0 of active dresing sq Active compounds compound in the applied anon means no mycelium growth, either on the treated subdressing in in glkg in strate or on the inoculum, the symbol means myceliy Weight Seed urn growth on the inoculum only, no spread to the treated substrate; and the symbol means mycelium non-dressed Zinc ethylene-bisgrowth from the inoculum on to the treated substrate, dithiocarbamate 10 5 similar to the spread to the untreated substrate of the H l 10 l 0.05 con 0 30 1 0.005

The active compounds, the concentration of the ac-' 40 tive compounds, the test fungi and the inhibition effects :3 5%? achieved canbe seen from the following Table l: 30 1 0,00 5

TABLE 1 Agar plate test Concentration of active coin- Corti- Verti- Thiela- Phytoph- Fusarium pound in suhcium Sclerotinia cillium viopxis thora Fusarium I 'usarium salami f. Activn compound strntainnpuu. rolfaii sclerottorum allmatrum lmaicnla cartormn culmonun oxyapormn pisi Untrentvd t loutm-hlomllitrobonzunu [(n) 11) ii (known) (A) v. v Hi) 10!] l) Zlur- 0H|yI0||0-l:Is-IiItl||0mlrlm- {(n) H) -1- i- IIHLIMUUIUWII) (Ii). (1)) I00 'i- (I 'I' i i Zlm:(Hml-tliyldl|.l|lm'm'lmnmin :(n) 10 I- -I- I (known) ((3) (h) (I .7 -lli Cl Cl (b) ll)" 0 (I 0 0 (l 0 0 0 iNH 1) Br Br {(21) 10 o o o o 0 0 o 0 (b) 100 0 0 o 0 0 o 0 0 HaC O ti-NH 2) o l i-NH (a) 7 .4 EXAMPLE 3 Soil Treating Agent Test/Soil-bome Mycoses To produce a suitable preparation of the active comthrough Pythium ultimum. The soil is filled into pots, each of which is sown with seeds of the wrinkled canning pea. The pots are placed in a greenhouse at l5l 8 and kept normally moist.

pound, the active compound is extended with talc to a 5 Three weeks after sowmg the number of healthy content of 5 percent and subsequently with quartz sand Plants deten'mhed as a Percentage of the number of to a content of 0.5 percent of active compound. Seeds Sewh- 0 Percent means that no healthy Plant has The preparation of the active compound is uniformly grown; 100 Percent means that healthy Plants have mixed with Fruhstorfer standard soil, which has first 10 resulted 'P the seedsbeen sterilized and then inoculated with pure cultures The active mp the eoheehtt'atlohs the f the test f i t1ve compounds 1n the s01], and the results obtained can The soil is filled into 5 pots, each of which is sown be Seen from the followmg Table with 10 seeds of the host plants. The pots are placed in TABLE 4 a greenhouse at the stated temperatures and kept nor- 1 5 mally moist. Soil treating agent test/Pythium ultimum 3 weeks after sowing, the number of healthy plants is N be r Active Concentration um r o determmed as a percentage of the number of seeds compounds of active heanhy plants sown. 0 percent means that no healthy plants have compoundin in grown; 100 percent means that healthy plants have mg/hte' resulted from all the seeds.

The active compounds, the concentrations of the acuntreated I0 3 tive compounds in the soil, the test fungi, host plants, 8 greenhouse temperatures and the results obtained can Tetramethylthiourambe seen from the following Table 3: 25' 3 2;

'I (known (D) EXAMPLE 4 1o 6 25 2 S i] T Zinc ethylene-bis- 50 6 reatlng Agent TestlPythlum Ultunum dithiocarbamate 100 6 To produce a suitable preparation of the active com- (Known 1 (B) 25 78 pound, the active compound is extended with talc to a 50 90 content of 5 percent and subsequently with quartz sand 1 20 32 to a content of 0.5 percent of active compound. (1

The preparation of the active compound is uniformly mated with naturally infected compost soil which, when 1 00 72 sown with wrinkled canning peas, is known from ex- (3) penence to lead to high losses among the seedlings TABLE 3 Seed treating agent test [soil-borne mycoses Number of healthy plants in percent.

Test fungi Fuaariu'm rrticill. Carticiym 'l'll ivlaviopris culmorum elboatrum rolfsii basirola Host plant Pea] Pea I Pea Cotton Concentration of Temperature range active compound 7 Active compounds in mg./liter soil 2225 2225 ZZZ-25 22-2525 Fruhstorier standard soil, sterilized, untreated 92 96 96 mi Fruhstorfer standard sii], sterilized and inoculated, untreated 6 6 0 0 10 s 20 25 22 2 Tetrmncthyltlnouram disulfide (known) (D) 16 18 22 u 100 42 22 30 (1 200 a4 c o 10 1o 30 a 22 25 14 20 22 32 14 2s 20 50 NSCC1: 34 as 40 46 200 46 (known) (E) 10 4 o 25 8 l] (I Zincothylenu-bisflithIneurbumute (known) (I!) 50 0 (i (l n 100 24 4 u C] 200 4 10 22 2s 74 52 me- 50 76 62 x4 72 i 100 2 as 114 200 x2 em N Nll 1 9 EXAMPLE Seed Dressing Test/Soilborne Mycoses To produce a suitable dry dressing, the active compound is extendedwith a mixture of equal parts by weight of talc and kieselguhr to give a-finely powdered mixture with the desired concentration of active compound.

To apply the dressing, the seeds of suitable host plants are shaken with the dry dressing in a closed glassv flask. Five batches of grains of the seed are sown in pots which contain Fruhstorfer standard soil which has first been sterilized and then inoculated with pure cul-' tures of the test fungi. The pots are placed in a greenhouse at the hereinafter-stated temperatures and are kept normally moist.

Three weeks after sowing, the number of healthy plants is determined as a percentage of the number of seeds sown. 0 percent means that no healthy plants have grown, whereas 100 percent means that healthy plants have resulted from all the seeds.

The active compounds, their concentrations in the dressing, the amounts of dressing used, test fungi, type of soil, host plants, greenhouse temperatures and the results obtained can be seen from the following Table 25 introduced, with stirring and cooling. The methylene chloride is distilled 011' and the residue is recrystallized from white spirit. 594 g 3-methyl-4,4- dichloropyrazolinone-(S) with a melting point of 113 C are obtained. The yield is 94.8 percent of the theory.

In analogous manner, the following active compoungs mentioned in the test Examples can be obtaine 10 Formula m.p.(( I) .Br Br It will be appreciated that the instant specification and examples are set forth by way of illustration and 5. not limitation, and that various modifications and TABLE 5 Seed dressing test/soil-borne mycoses Test fungus: Fuaarium culmnrum Host plant: Pea Temperature range: 22-2b Concentration of active compound in the dressing Dressing] in percent seed, Number of healthy plants Active compounds by weight gJkg. in percent Fruhstorier standard soil, sterilized, n0n-dressed 92 Fruhstorfer standard soil, sterilized and inoculated, non-dressed 22 Tetramethylthiouram disulfide (known) (D) 50 2 43 C O 5 2 12 25 2 38 2 14 N-S-C C l: 75 2 32 (known) (E) Zinc ethylene-bis-dithiocarbamate (known) (B) 70 2 24 C1 Cl 10 2 63 30 2 73 30 4 78 H3C- -O N--NH (1) The following Example illustrates, without limitation, the preparation of the compounds used according to the present invention.

EXAMPLE 6 370 g 3-methylpyrazolinone-(5) are suspended in 1.5 liters of methylene chloride in a three-necked flask which is equipped with an introduction tube, a reflux condenser and a thermometer, and 540 g chlorine are in which each X individually is halogen, and

R is hydrogen, alkyl with up to 24 carbon atoms optionally carrying 1 1 12 up to three halo substituents or phenyl optionally C1 C1 carrying a substituent selected from the group consisting of methoxy and nitro, -O in admixture with an inert solid pesticide diluent or ex- J tender. 5 M f 2. The composition of claim 1 wherein each X in- The com f dividually is fluorine, chlorine or bromine and R is 95 5 2 2 335 gfl ig gfigggfi l to Y alkyl wlth p to 17 carboll atoms 7. A method of combating fungi which comprises apmchloromethyl, p y methoxy-phenyl or mtrophenw plying to the fungi or a fungus habitat a fungicidally efyl. fectlve amount of halopyrazolinone of the 3. The composition of claim 1, wherein the active ingredient is 3-methyl'4,4-dichloro-pyrazolinone-(5) of the formula x x 4. The composition of claim 1, wherein the active in- 20 gredient is 3-methyl-4,4-dibromo-pyrazolinone-(5) of the formula in which each X individually is halogen, and

R is hydrogen, alkyl with up to 24 atoms optionally v carrying up to three halo substituents or phenyl Br B optionally carrying a substituent selected from the group consisting of methoxy and nitro.

H5 I 25 8. The method of claim 7 wherein said NH (2) halopyrazolinone is 3-methyl-4,4-dichloropyrazolinonc-(5),

3-methyl-4,4-dibromopyrazolinone-(5) or 5. The composition of claim 1, wherein the active in- 4,4-dichloropyrazolinone-(5). gredient is 4,4-dichloropyra2olinone-(5)of the formula UNHI'ID S'I'A'IICS PA'IEN'F OFFICE CERTIFICATE OF CORRECTlON Patent No. 686,410 I Dated A g st 2 1972 I Invcntor(s) Kurt Findeisen .et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C01. 6 Table 2 Rewrite last 5 lines of Table under heading "Active Compounds" which were omitted:

I N... ....NH

Br Br 0 0 l N .NH

UNITED STA'I'IIS PA'lIINT ()FFKE CEH'lIFlC/KTE 0F CORREC' H.ON

Patent No. 3 Dated I August 22 1972 Inventor(s) Kurt: Findeisen et a1 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below;

Col. 7 Table 3 Second entry under "Active Compounds" "siil" should be soil Col. 8 line 4 I "l5-l8" should be l5-18 Col. 8, line 32 in Table 4 "2.00" should be under "100" Signed and sealed this'ZSrd day of January 1973.,

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSC HALK Attesting Officer Commissioner of Patents 

2. The composition of claim 1 wherein each X individually is fluorine, chlorine or bromine and R is hydrogen, alkyl with up to 17 carbon atoms, trichloromethyl, phenyl, methoxy-phenyl or nitrophenyl.
 3. The composition of claim 1, wherein the active ingredient is 3-methyl-4,4-dichloro-pyrazolinone-(5) of the formula
 4. The composition of claim 1, wherein the active ingredient is 3-methyl-4,4-dibromo-pyrazolinone-(5) of the formula
 5. The composition of claim 1, wherein the active ingredient is 4,4-dichloropyrazolinone-(5) of the formula
 6. The composition of claim 1 containing from 1 to 95 percent of the active compound, by weight.
 7. A method of combating fungi which comprises applying to the fungi or a fungus habitat a fungicidally effective amount of halopyrazolinone of the in which each X individually is halogen, and R is hydrogen, alkyl with up to 24 atoms optionally carrying up to three halo substituents or phenyl optionally carrying a substituent selected from the group consisting of methoxy and nitro.
 8. The method of claim 7 wherein said halopyrazolinone is 3-methyl-4,4-dichloropyrazolinone-(5), 3-methyl-4,4-dibromopyrazolinone-(5) or 4,4-dichloropyrazolinone-(5). 